Polystyrene-Grafted Silica Nanoparticles - American Chemical Society

Feb 15, 2017 - We synthesized polystyrene-grafted silica nanoparticles (Si-PS) via ARGET ATRP .... Here, we investigate glass transition behavior of S...
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Polystyrene-Grafted Silica Nanoparticles: Investigating the Molecular Weight Dependence of Glass Transition and Fragility Behavior Shadid Askar,† Lingqiao Li,† and John M. Torkelson*,†,‡ †

Department of Chemical and Biological Engineering and ‡Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States ABSTRACT: Polymer-tethered nanoparticles provide a strategy to improve particle dispersion in polymer nanocomposites and as materials themselves can exhibit self-healing behavior and enhanced mechanical properties. The few studies that previously characterized the glass transition temperature (Tg) behavior of neat polymer-grafted nanoparticles in the absence of a polymer matrix largely focused on average Tg response. We synthesized polystyrene-grafted silica nanoparticles (Si-PS) via ARGET ATRP, achieving the densely grafted state. Using differential scanning calorimetry, we investigated the brush molecular weight (MW) dependence of Tg, Tg breadth, heat capacity jump (ΔCp), and fragility from 12 to 98 kg/mol. Compared with free PS chains of the same MW, brush Tg increases by 1−2 °C, brush Tg breadth remains unchanged within error down to 36 kg/mol and increases by 3−4 °C at brush MWs of 12 and 13 kg/mol, and brush ΔCp and fragility remain unchanged within error down to 52 kg/mol and then decrease with decreasing MW. Evidence of a significant Tg gradient from near the nanoparticle graft interface to near the free chain end was obtained for the first time via fluorescence of a pyrenyl dye labeled at specific regions along the brush chain length. In relatively high MW brushes, Tg = ∼116 °C near the graft interface and Tg = ∼102 °C near the chain end. Comparisons are made to results recently reported for similar PS brushes densely grafted to a flat substrate, which indicate that a larger Tg gradient is evident in a grafting geometry involving a flat interface as compared with a spherical nanoparticle interface. Other comparisons are also made with glass transition and fragility behaviors reported in the flat substrate geometry. Results of this study and others will help to better understand nanocomposites and tailor them for optimal properties.

1. INTRODUCTION Nanofillers are commonly added to polymers to yield nanocomposites with enhanced thermal, optical, and mechanical properties relative to neat polymer.1−29 Many of the property enhancements associated with nanocomposites have been explained as arising from how interphase regions of polymer located near nanofiller interfaces are perturbed by the nanofiller.30−34 Such interfacial perturbations are also considered to be an origin of confinement effects, i.e., when polymers are confined to nanoscale dimensions as in supported thin films or nanotubes.35,36 A critical consideration in optimizing and understanding nanocomposite behavior is that significant nanoparticle aggregation may hinder property enhancements associated with the presence of nanofillers. One approach to improve particle dispersion involves utilizing polymer-grafted nanoparticles or hairy nanoparticles, which in certain instances can exhibit enhanced compatibility with the surrounding polymer matrix.17,37−45 Polymer-grafted nanoparticles themselves have exhibited interesting self-healing behavior and enhanced mechanical properties.46−48 Many reports in the literature have investigated the glass transition temperature (Tg) behavior of nanocomposites containing polymer-grafted nanoparticles within a polymer matrix.12,49−57 However, under conditions of dense grafting, © XXXX American Chemical Society

polymer-grafted nanoparticles exhibit notable Tg behavior themselves.38−45,48,58 Savin et al.39 reported reductions in Tg of polystyrene-grafted silica nanoparticles (Si-PS) with decreasing graft molecular weight (MW). In particular, Tg = 101 ± 1 °C for Si-PS with graft MWs between 32.7 and 15.0 kg/mol and 94 ± 1 °C for Si-PS with graft Mn = 5.2 kg/mol. In agreement with Savin et al.,39 Dang et al.40 reported reductions in Tg from 105.5 to 94 °C in Si-PS with reductions in graft MW from ∼200 to ∼10 kg/mol, respectively. Kim et al.41 investigated the Tg of cis-1,4-polyisoprene-grafted silica nanoparticles (Si-PI). Although they did not specifically comment on the MW dependence of Tg in Si-PI samples, the data indicate that Tg decreases with decreasing MW. These reports are in agreement that at the same MW grafted polymers exhibit enhanced Tg relative to free polymer chains.38−41 In addition to brushes grafted from spherical nanoparticles, brushes may also be grafted from flat silica substrates.59,60 Lan and Torkelson60 demonstrated via ellipsometry that dense PS brushes grown from flat silica substrates exhibit no MW dependence of average Tg down to 23 kg/mol. Interestingly, Tg Received: January 12, 2017 Revised: February 9, 2017

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2.3. Synthesis of Polymer Brushes. Dense PS brushes were synthesized by activator regenerated by electron transfer (ARGET) ATRP.67 Functionalized silica nanoparticles (0.2 g) were dispersed into a solution containing tris(2-pyridylmethyl)amine (3.0 mg), copper(II) bromide (0.5 mg in 0.2 mL of dimethylformamide), methyl α-bromoisobutyrate (3.0 μL), styrene (5.0 mL), dimethylformamide (2.0 mL) and tin(II) 2-ethylhexanoate (60 mg). The mixtures were purged using nitrogen for 20 min prior to polymerization at 85 °C for various times. After polymerization, the mixtures were immediately precipitated into excess methanol. The Si-PS samples were recovered via centrifugation and washed with toluene at least three times to remove ungrafted PS chains. In some cases, PS brushes were also labeled for fluorescence measurements at various distances from the particle interface. Labeling was achieved by adding trace amounts of 1-pyrenylbutyl methacrylate (BPy) into styrene before ARGET ATRP. Two labeled samples were polymerized via chain extension where in one the fluorescent label was located within 8 kg/mol of the graft interface (total brush Mn = 54 kg/ mol) and in the other the label was located within 14 kg/mol of the free chain ends (total brush Mn = 93 kg/mol). This labeling was achieved via the following chain extension procedure. Brushes were first grown from the nanoparticle surfaces for the desired length of time. After polymerization, the grafted nanoparticles were precipitated in methanol and purified via centrifugation and resuspension in toluene three times. After removing unreacted monomer and ungrafted chains, the grafted nanoparticles were used as macroinitiators to perform chain extension through ARGET ATRP for the desired length of time. A similar chain extension procedure was used for brushes grafted to flat silica substrates.60 The resulting polymergrafted nanoparticles were again recovered and purified via centrifugation. As determined via UV/vis absorbance spectroscopy (PerkinElmer), the label contents are 0.9 or 1.1 mol % within the labeled portions of the brushes with Mn = 8 or 14 kg/mol, respectively, as determined from the unattached labeled chains. 2.4. Characterization of Si-PS Samples. Gel permeation chromatography (GPC) (Waters 2410, light scattering detector (Wyatt)) was used for characterizing MW and dispersity of free polymer chains. (We note that free initiator methyl α-bromoisobutyrate was used to polymerize ungrafted PS chains simultaneously with the grafted chains. This was done for MW characterization of grafted chains. It has been reported previously that the number-average MWs (Mn)s of free and grafted chains are equal.67,68) The Mn values ranged from 12 to 98 kg/mol with an average dispersity = 1.1 ± 0.1. All Mn values of polymers reported in this study were determined via light scattering detection (using dn/dc = 0.184 mL/g for PS in tetrahydrofuran). Thermogravimetric analysis was used to determine the graft density of the PS brushes on silica nanoparticles. The portion of PS in Si-PS samples decreases from 96 to 55 wt % in Si-PS with reductions in graft Mn from 98 to 12 kg/mol. Graft densities are tabulated in the Results and Discussion. 2.5. Differential Scanning Calorimetry Measurements. DSC (Mettler-Toledo 822) was used to characterize Tg, Tg breadth, and fragility of PS and Si-PS samples. Samples were first annealed for 10 min above bulk Tg at 140 °C and then cooled to 40 °C at a cooling rate of −40 °C/min. Tg values were determined by the onset upon heating at a rate of 10 °C/min from 40 to 140 °C. Tg breadth values were determined from first-derivative heat flow curves, which involved taking the derivative of heat capacity curves with respect to temperature.69−71 Fragility values were determined from the cooling rate dependence of fictive temperature (Tf) using rates ranging from −0.4 to −40 °C/min followed by heating at 10 °C/ min;72−77 Tf was evaluated using the Richardson method.78 The fragility, m, can be determined from eq 1:73,75

breadth (as measured by ellipsometry) increased from 20 to 35 °C with decreasing brush MW from 170 to 23 kg/mol.60 With decreasing brush molecular weight, the enhancement in Tg breadth coupled with the lack of change in average Tg across the length of the dense brushes indicates that the overall average Tg is a reflection of the combined perturbation to local Tg originating from grafted and free chain ends. We note that there is no published report on the Tg breadth of PS-grafted nanoparticles as a function of graft MW. Nanocomposite fragility can be affected by the addition of bare nanofillers.61−65 Using simulations, Betancourt et al.65 have reported that in the case of bare nanoparticles attractive interactions with the polymer matrix cause enhancements in fragility and nonattractive interactions with the polymer matrix cause reductions in fragility.65 Only one experimental report49 has investigated the impact of polymer-grafted nanoparticles on the fragility of nanocomposites, in particular, PS grafted onto gold nanoparticles (Au-PS) dispersed in a PS matrix. Although the reported changes were small, the data suggested that the grafted nanoparticles caused reductions in fragility relative to neat PS and that the fragility of Au-PS exhibited MW dependence.49 There is no published report of fragility in polymer-grafted nanoparticles without a host matrix. Here, we investigate glass transition behavior of Si-PS nanoparticles without a host matrix. Tg measurements are obtained as a function of graft MW and are compared with other reports in the research literature. We also provide the first comparison of Tg breadth in polymer-grafted nanoparticles as a function of MW with that in brushes grown from flat substrates. Fluorescence spectroscopy is also used to investigate local Tg as a function of distance from the grafting interface, i.e., the Tg gradient. The MW dependence of fragility in Si-PS is investigated using differential scanning calorimetry (DSC).

2. EXPERIMENTAL SECTION 2.1. Materials. Styrene monomer (Sigma, 99.9%) was deinhibited using calcium hydride (Sigma, 90%) and inhibitor remover (Sigma, 311340) before polymerization. Toluene (Fisher, 99.5%) and dimethylformamide (Fisher, 99.9%) were dried over activated molecular sieves (Sigma, 208574) before use. Silica nanoparticles (Nissan Chemical, MEK-ST) with reported particle diameters of 10− 15 nm were obtained as a dispersion (30 wt % in methyl ethyl ketone) and resuspended in dry toluene via solvent exchange. 1-Pyrenylbutyl methacrylate monomers were synthesized as described by Ellison and Torkelson.66 An anionically synthesized PS standard (Polymer Science, 400 kg/mol, dispersity = 1.06), (3-aminopropyl)triethoxysilane (Sigma, 98%), triethylamine (Sigma, 99%), α-bromoisobutyryl bromide (Sigma, 98%), tris(2-pyridylmethyl)amine (Sigma, 98%), copper(II) bromide (Sigma, 99%), methyl α-bromoisobutyrate (Sigma, 99%), methanol (Fisher), and tetrahydrofuran (Fisher) were used as received. 2.2. Surface Functionalization of Silica Nanoparticles with Initiator. (3-Aminopropyl)triethoxysilane (0.40 mL) was added dropwise to a mixture of silica nanoparticles (3.0 g) and dry toluene (10.0 mL) that was subjected to rigorous mixing and maintained under a nitrogen atmosphere. The mixture was then heated to reflux temperature (60 °C) and reacted for 12 h. To purify, the aminefunctionalized silica nanoparticles were centrifuged and resuspended in toluene three times. Under rigorous mixing, the atom transfer radical polymerization (ATRP) initiator (α-bromoisobutyryl bromide) (4.0 mL) was added dropwise to a solution containing amine-functionalized silica nanoparticles (2.0 g), triethylamine (4.0 mL), and dry toluene (30.0 mL) at 0 °C. The resulting mixture was sealed and reacted ∼12 h under ambient conditions. To purify, the ATRP initiator-grafted nanoparticles were recovered via centrifugation and resuspended in ethanol three times.

log(Q /Q s) = m − m(Tf s/Tf )

(1)

where Q is the cooling rate, Qs is a standard cooling rate of 10 °C/min, and Tfs is the fictive temperature for the standard cooling rate. The reported errors for fragility are standard deviations from at least three determinations. B

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for Si-PS with varying brush MW. The scaled heat flow is calculated by dividing the temperature-dependent heat capacity curves by the mass of PS in the Si-PS samples. Figure 2A shows that Tg,onset values decrease as graft MW decreases. In particular, the Si-PS samples exhibit reductions in Tg,onset from 104.5 ± 0.5 to 97.7 ± 0.4 °C with reductions in graft Mn from 98 to 12 kg/ mol. (Our Tg,onset data are summarized in Table 1.) Savin et al.39 report Tg = 101 ± 1 °C for Si-PS with graft MWs between 32.7 and 15.0 kg/mol and 94 ± 1 °C for Si-PS with graft Mn = 5.2 kg/mol. (Savin et al.39 used the Richardson method78 to measure fictive temperature (Tf) values from DSC heat flow curves, which they report as Tg values. The fictive temperature is defined as the point at which a glass would transition to a rubbery equilibrium state upon sufficiently rapid heating from the nonequilibrium glassy state.77,84) In addition, Dang et al.40 report reductions in Tg from 105.5 °C in Si-PS 200 kg/mol to 94 °C in Si-PS 10 kg/mol. (Dang et al.40 measured Tg,onset values from DSC heat flow curves.) Figure 2A also indicates that for the lowest MW brushes in this study (Si-PS 12 and 13 kg/mol) the step change in heat capacity (ΔCp) is smaller than that in higher MW brushes. This contrasts with PS free chains, which exhibit no reduction in ΔCp within error with decreasing MW for the MW range studied. We note that ΔCp values for PS free chains are within error equal to those for Si-PS with sufficiently high MW (see Table 1). Reductions in ΔCp with decreasing MW have been noted in other reports of bare silica nanoparticles within a polymer matrix.18,86 With increasing silica content, the reduction in ΔCp in such nanocomposites has been attributed to the immobilization of polymer in the interfacial region near the nanofiller, which restricts participation in the glass transition. This description may also apply to our two lowest MW Si-PS systems, where a sizable fraction of the PS brushes does not apparently participate robustly in the glass transition. Figures 2B and 2C show in full detail how Tg,onset and Tf values decrease with decreasing MW for both Si-PS and PS free chains. The MW dependence observed in our study is in major agreement with both Savin et al.39 and Dang et al.40 Reductions in Tg can be attributed to enhanced influence from free chain ends at low MW. Zhang and Torkelson87 recently stated that “the role of chain ends in providing a greater degree of conformational freedom is central to the MW dependence of Tg.” This is because free chain ends enhance free volume and configurational entropy of the polymer chains.87−92 As MW decreases, enhanced configurational freedom provided by free chain ends reduces requirements for cooperative mobility and hence Tg decreases. In the case of Si-PS, one end of the chains is immobilized. The immobilization causes an enhancement in Tg relative to PS free chains of the same MW. These results are in agreement with reports in the literature,38−41 which indicate that tethering and chain confinement cause elevated Tg in the grafted chains relative to free chains. In understanding the MW dependence of Tg, one might simply compare the Tg of grafted chains with the Tg of free chains with twice the MW since the concentration of free chain ends would be the same. However, such a simplistic comparison does not capture differences in chain end effects associated with Si-PS and unattached PS. In the case of Si-PS, the free chain ends are concentrated away from the grafting interfaces of the nanoparticles, whereas in the case of unattached PS, the free chain ends are evenly dispersed throughout the polymer. The influence of free chain ends on cooperative mobility and packing efficiency is investigated further in a later discussion of fragility results.

2.6. Fluorescence Measurements. The Tg values of labeled SiPS samples were characterized via fluorescence spectroscopy (Photon Technology International). Si-PS samples were suspended in toluene and drop-cast onto glass slides. After allowing excess toluene to evaporate under ambient conditions, labeled Si-PS samples were annealed at 120 °C for 3 h prior to fluorescence measurements. Samples were then transferred to a heating stage at 145 °C and held for 20 min. Emission spectra were collected from 370 to 405 nm (excitation at 324 nm, 1 s integration time) using 0.5 mm slit widths (1 nm bandpass). Samples were cooled from 145 to 60 °C at 1 °C/ min, and spectra were collected every 2.5 °C. Normalized integrated intensity was plotted as a function of temperature, and the Tg was determined by the intersection of lines fitted through the rubbery and glassy temperature dependences of normalized intensity.60,77,79−82 The best-fit lines were obtained by fitting data in the glassy and rubbery regimes beginning with the lowest and highest temperature values. Points were added to the fits until the fit lines no longer passed through the data points, i.e., R2 < 0.990. 2.7. Scanning Electron Microscopy. PS-grafted nanoparticles were dispersed in toluene and then drop casted on an alumina scanning electron microscopy stage. The samples were then dried in vacuum overnight before characterization. A Hitachi SU8030 scanning electron microscope equipped with a cold field emission gun was used to characterize the microstructure of Si-PS samples.

3. RESULTS AND DISCUSSION Figure 1 shows a typical field-emission scanning electron microscopy (SEM) image of PS-grafted silica nanoparticles with

Figure 1. Scanning electron micrograph of PS-grafted nanoparticles with a brush molecular weight of 12 kg/mol (left) and the chemical structure of the attachment (right). Silica nanoparticles have diameters of 10−15 nm. The scale bar in the SEM image is 50 nm.

graft Mn = 12 kg/mol; the SEM samples were prepared in a manner similar to that described by Savin et al.39,83 The schematic on the right in Figure 1 illustrates the molecular details of how PS is linked to the silica nanoparticle surface. In the SEM image, dark spheres represent silica nanoparticles and the lighter-color spacing between the particles indicates the presence of PS separating the nanoparticles. In a study by Savin et al.,39 transmission electron microscopy (TEM) images were presented for Si-PS samples of varying graft MW (unmodified silica nanoparticles were obtained from the same provider as employed here, Nissan Chemical, and had a reported average measured diameter of 20 nm39). In particular, the TEM image for Si-PS with graft Mn = 15 kg/mol from Savin et al.39 appears nearly identical to Figure 1, indicating that successful grafting was achieved in this study. Figure 1 also shows that the interparticle spacing between silica spheres is ≲20 nm, and thus the PS grafts are nanoconfined. DSC is used to investigate Tg behavior of Si-PS samples. Figure 2A shows scaled heat flow as a function of temperature C

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Figure 2. (A) Scaled heat capacity as a function of temperature for PS-grafted silica nanoparticles (Si-PS) with graft molecular weights ranging from 12 to 98 kg/mol. The heat capacities were divided by the mass of polymer in the samples. (B) Onset Tg values as a function of molecular weight for Si-PS samples (triangles) and PS free chains (circles). Tg,onset values were determined by intersection of lines shown in (A). (C) shows Tf values for the same samples shown in (B). Tf values were determined by the Richardson method78 after cooling the samples at −40 °C/min and heating at 10 °C/min.

Table 1. Property Summary for PS-Grafted Silica Nanoparticles and PS Free Chains as a Function of Molecular Weight brush Mn (kg/mol)

polymer weight fraction

12 13 36 52 70 98 free chain Mn (kg/mol)

0.55 0.57 0.72 0.83 0.92 0.96 polymer weight fraction

0.40 0.36 0.28 0.36 0.46 0.6285,c grafting density (chain/nm2)

12 13 36 52 90 400b

− − − − − −

− − − − − −

ΔCp,brush (J/(g K))

grafting density (chain/nm2)

0.10 0.19 0.20 0.24 0.24 0.24

± ± ± ± ± ±

0.03 0.02 0.01 0.02 0.01 0.01

ΔCp,free chain (J/(g K)) 0.23 0.25 0.25 0.27 0.28 0.26

± ± ± ± ± ±

brush Tg,onset (°C)

0.02 0.02 0.01 0.01 0.02 0.01

brush Tg breadth (°C)

97.7 ± 0.4 16.0 ± 0.5 99.1 ± 0.3 15.3 ± 0.4 101.9 ± 0.5 13.4 ± 0.6 103.0 ± 0.5 12.4 ± 0.5 104.1 ± 0.4 13.4 ± 0.3 104.5 ± 0.5 12.7 ± 0.5 free chain Tg,onset free chain Tg breadth (°C) (°C) 96.2 97.1 100.8 102.0 102.0 102.0

± ± ± ± ± ±

0.6 0.4 0.5 0.4 0.5 0.5

12.3 12.7 12.5 12.7 12.9 12.6

± ± ± ± ± ±

0.5 0.6 0.4 0.4 0.6 0.5

brush Tfa (°C) 98.3 ± 0.5 99.4 ± 0.6 102.0 ± 0.3 103.2 ± 0.4 103.8 ± 0.3 104.1 ± 0.5 free chain Tfa (°C) 96.6 97.2 100.9 101.8 102.2 102.3

± ± ± ± ± ±

0.6 0.4 0.4 0.5 0.4 0.4

brush fragility, m 119 ± 9 121 ± 7 130 ± 5 144 ± 9 148 ± 8 156 ± 9 free chain fragility, m 140 143 150 157 158 163

± ± ± ± ± ±

7 9 6 8 8 10

Fictive temperature values were determined from the Richardson method.78 Samples were characterized after cooling at −40 °C/min and heating at 10 °C/min, identical to the method used to determine Tg,onset values. bAnionically synthesized PS standard. cThis is an apparent grafting density value. See ref 85.

a

The breadth of the glass transition is also investigated using DSC. Figure 3A shows scaled first derivative heat flow curves as a function of temperature for Si-PS with varying brush MW. These curves are obtained by taking the derivative (with respect to temperature) of the heat flow curves shown in Figure 2A. T0 values are determined by the onset of deviations from baseline behavior of the scaled first-derivative heat flow curves, and Te

values are determined from temperatures at which minima are observed in the first-derivative heat flow curves after the transition.69−71 The Tg breadth is determined from Te − T0, and the values associated with Si-PS samples are plotted in Figure 3B. Relative to Si-PS 98 kg/mol, which exhibits a breadth of 12.7 ± 0.5 °C, Tg breadth remains invariant with graft MW down to 36 kg/mol and increases to 15.3 ± 0.4 and D

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Figure 3. (A) Scaled first derivative heat flow as a function of temperature for Si-PS samples with graft molecular weights ranging from 12 to 98 kg/ mol. T0 values are shown by the intersection of lines depicting deviation from baseline behavior, and Te values are indicated by down arrows. (B) Tg breadth as a function of graft molecular weight. Tg breadths were calculated via Te − T0 from (A).

16.0 ± 0.5 °C for graft MWs of 13 and 12 kg/mol, respectively. While both T0 and Te values decrease in the lowest MW Si-PS samples, the enhancement in Tg breadth in such cases can be attributed to greater reductions in T0 values relative to Te values. This suggests that as brush MW decreases, enhancements in configurational freedom provided by the high concentration of free chain ends in regions away from the nanoparticle interface becomes stronger. For unattached PS, Tg breadths are invariant with MW for the MW range studied and identical within error to the Tg breadth of high MW Si-PS. (See Table 1 for a summary of Tg breadth data.) Results for Tg breadth of PS brushes grafted from silica nanoparticles may be compared with those of PS brushes grafted from flat silica substrates.60 Using ellipsometry, Lan and Torkelson60 reported that Tg breadth of PS grafts increased from 20 to 35 °C with reduced graft Mn from 170 to 23 kg/ mol. The results of the present study are in agreement that the Tg breadth increases with decreasing graft MW. Quantitative differences in the results can be attributed to differences in geometry between brushes on highly curved spherical nanoparticles and flat substrates. (They cannot be attributed to the different measurement methods because the Tg breadths for 470 kg/mol PS as measured by DSC and ellipsometry were reported to be the same within error.69) For instance, in the spherical geometry, polymer grafts experience greater conformational freedom with increasing distance from the interface. The influence of the substrate is apparent until the polymer grafts exhibit random coil-like conformations far from the grafting interface. In contrast, the influence of the substrate extends to greater lengths along the polymer chains in brushes grafted from flat substrates. This is why Lan and Torkelson60 observed greater T+ values (from ellipsometry) compared to Te values (from DSC) in this study. Geometry also impacts the influence of free-surface effects on Tg behavior. In Si-PS, there are no true free surfaces. Thus, reductions in T0 as observed via DSC are associated only with free chain-end effects. In contrast, in the case of dense brushes on a flat substrate, free chain ends are in contact with or very close to a free surface. As MW decreases, free-surface effects coupled with the enhanced conformational freedom provided by free chain ends cause substantial reductions in T− as observed via ellipsometry. The enhancement in T+ relative to Te and

reduction in T− relative to T0 due to sample geometry explains the greater Tg breadth observed in brushes on flat substrates than in brushes on spherical nanoparticles. We also note that our DSC results comparing Tg responses of Si-PS nanoparticles with those of neat polymer as a function of PS MW differ from those reported by Holt et al.58 for silica nanoparticles densely grafted with poly(2-vinylpyridine), Si− P2VP. Relative to neat P2VP, the Tg of Si−P2VP exhibited ∼9 and ∼12−13 K increases for 18 and 6 kg/mol P2VP, respectively. Additionally, the 6 kg/mol Si−P2VP exhibited a very substantial increase in glass transition breadth relative to neat P2VP of the same MW. Future studies investigating the polymer species dependent Tg behavior in densely grafted brushes are warranted. Fluorescence spectroscopy is used to investigate local Tg values in dense Si-PS brushes with high MW. Figure 4 shows the normalized integrated intensity as a function of temperature

Figure 4. Normalized integrated intensity as a function of temperature for end-labeled Si-PS. Intensity values were normalized to the maximum intensity value and shifted arbitrarily for clarity. Open triangles represent Si-PS with 1-pyrenylbutyl methacrylate (BPy) labeling within 14 kg/mol of the free chain ends (total brush Mn = 93 kg/mol). Open squares represent Si-PS with BPy labeling within 8 kg/ mol of the graft interface (total brush Mn = 54 kg/mol). Arrows indicate the location of Tg determined by the intersection of lines fitted to the rubbery and glassy temperature dependences of intensity. E

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Figure 5. (A) Log(Q/Qs) as a function of Tfs/Tf for 400 kg/mol PS and Si-PS 12 kg/mol. The negative of the slope is fragility (eq 1). (B) Fragility as a function of molecular weight for PS free chains (open squares) and Si-PS (closed triangles). The dotted and dashed lines correspond to the average fragility and standard deviation of a 400 kg/mol PS standard. The data points denote average values from three sample determinations of m, and error bars are associated with the standard deviation of three trials for each sample.

is stronger than the polymer−polymer interaction, a “bound” polymer layer is adsorbed to the nanoparticle (NP) surface. “This bound layer “cloaks” the NPs, so that the dynamics are largely unaffected. Consequently, Tg defined from the temperature dependence of routinely measured thermodynamics or the polymer matrix relaxation is nearly independent of [this interaction strength], in accord with many experiments. Apparently, quasi-thermodynamic measurements do not reliably reflect dynamical changes in the bound layer, which alter the overall composite dynamics...care is required to separate the matrix and bound components of the relaxation.”93 While our Si-PS system does not possess such interaction strength, many other Si-based nanocomposites do, e.g., with poly(methyl methacrylate) or P2VP as the matrix (and potential grafted polymer). The fluorescence approaches described above for monitoring Tg as a function of distance along a grafted chain could also be applied with nanoparticles exhibiting strong interactions with the polymer and with nanoparticles sparsely grafted with dye-labeled polymer (“hairy” nanoparticles). Such approaches could be used in the future to interrogate both Tg and stiffness94 effects in “bound” layers. Fragility behavior of Si-PS without a host matrix is also investigated using DSC. Figure 5A shows log(Q/Qs) as a function of Tfs/Tf for a 400 kg/mol PS standard and Si-PS 12 kg/mol. The cooling rates (Q) are −40, −20, −10, −4, −1, and −0.4 °C/min, and the standard cooling rate Qs = −10 °C/min. Fictive temperature values are determined via DSC using the Richardson method,78 and Tfs corresponds to the fictive temperature after cooling at the standard rate. The negative of the slope of a best-fit line in Figure 5A is the fragility (see eq 1). For the two examples shown, fragility values are 160 and 110 for a 400 kg/mol PS standard and Si-PS 12 kg/mol sample, respectively. Plots like Figure 5A are used to determine fragility values for all samples in this study. Each sample is measured at least three times to obtain averages and standard deviations. Figure 5B shows fragility as a function of MW for Si-PS and PS free chains determined via DSC. (Results are also summarized in Table 1.) The dotted line corresponds to the average fragility value of a 400 kg/mol PS standard. In PS free chains, fragility decreases from 163 ± 10 in 400 kg/mol PS to 140 ± 7 in 12 kg/mol PS. The reduction in fragility with decreasing MW in PS free chains is in agreement with values in the literature.95 In Si-PS, fragility decreases from 156 ± 9 in SiPS 98 kg/mol to 119 ± 9 in Si-PS 12 kg/mol. Thus, the fragility

for two samples. Lines fitted to the rubbery and glassy temperature dependences of integrated intensity yield Tg.60,77,79−82 Open squares represent the data for grafted PS chains where the 1-pyrenylbutyl methacrylate (BPy) label is incorporated in trace amounts within 8 kg/mol of the graft interface (total graft Mn = 54 kg/mol), with local Tg = ∼116 °C. Open triangles represent the data for grafted PS chains where the BPy label is incorporated within 14 kg/mol of the free chain ends (total graft Mn = 93 kg/mol), with local Tg = ∼102 °C. The fluorescence approach yields local Tg values that agree quantitatively with T0 and Te values determined via DSC for Si-PS with high brush MW (Figure 3A). Based on Figure 2A, the Si-PS 54 kg/mol and Si-PS 93 kg/mol samples would be expected to yield the same overall average Tg to within 1 °C, with Tg ≈ 104 °C. This suggests that in high-MW cases the fraction of the PS grafts with enhanced local Tg near the graft interface is small relative to the fraction of the PS grafts exhibiting bulk-like behavior. In low-MW brush cases, reductions in average Tg as observed by DSC can be attributed to increasing influence of free chain end effects. The fluorescence results may be compared with those from Lan and Torkelson,60 who conducted similar experiments on PS grafted from flat silica substrates. They observed Tg = 136 °C near the graft interface and Tg = 86 °C near the free chain ends. The higher Tg near the flat substrate relative to that near the nanoparticle can be attributed to brush geometry. As mentioned in the discussion of Figure 3, the impact of dense grafting is retained to greater lengths along brushes in the case of flat substrates (relative to spherical nanoparticles) since polymer chains do not experience a large change in local conformation as a function of distance from the graft interface. The lower Tg in the free chain ends associated with a flat substrate relative to that in nanoparticles can be attributed to free-surface effects. In the case of flat substrates, the free chain ends are in contact with or very near a free surface, whereas in the case of nanoparticles there is no true free surface. These results demonstrate that grafting geometry impacts local Tg behavior. Besides nanoparticle or substrate geometry, polymer− nanoparticle interfacial interactions are also expected to strongly influence the properties of polymer-grafted nanoparticles (PNGs) as well as nanocomposites made with PNGs or ungrafted nanoparticles. As recently noted by Starr et al.,93 when the polymer−nanoparticle interaction in nanocomposites F

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ellipsometry, Lan and Torkelson103 reported that fragility is independent of dense brush thickness down to 27 nm (Mn = 45 kg/mol). In this range, reducing the thickness and hence MW “does not significantly alter packing frustration in dense PS brushes.”103 The results in this study are in agreement, where significant changes in fragility are only observed for brush MWs at 36 kg/mol and below. For sufficiently low-MW brushes in SiPS, the impact of free chain ends in enhancing conformational mobility increases. This enables more efficient packing and thus reduced fragility in the low-MW polymer chains grafted from spherical nanoparticles.

of Si-PS 98 kg/mol is within error the same as that of high MW PS free chains. A comparison of 52 kg/mol Si-PS and PS free chains reveals that they both exhibit the same fragility values within experimental error. At 36 kg/mol, Si-PS exhibits significantly reduced fragility relative to PS free chains with the latter exhibiting no change within error from 400 kg/mol PS samples. At 13 and 12 kg/mol, both Si-PS and PS free chains exhibit reduced fragility (outside error) relative to 400 kg/mol PS free chains, with Si-PS exhibiting greater reductions. The data in Figure 5B indicate that grafting from spherical nanoparticles plays an important role in fragility behavior. In SiPS, the free chain ends are concentrated in the spacing between neighboring Si-PS particles.96 As MW decreases, free chain ends influence chain packing to a greater extent. As mentioned in the discussion of Figure 2, reduction in MW introduces free volume and conformational mobility via free chain-end effects. Enhancements in conformational freedom allow chains to pack more efficiently, which reduces fragility.87,97−99 Figure 5B shows that PS free chains exhibit a weaker MW dependence of fragility than Si-PS. This can be attributed to the fact that free chain ends are randomly dispersed throughout the polymer in unattached PS. While a reduction in MW enhances the concentration of free chain ends, the impact on conformational freedom in unattached PS is less than that in Si-PS. We also note that stronger glass formation and reduced Tg in Si-PS is indicative of antiplasticization behavior as indicated by other reports.49,100 Although this is the first experimental characterization of fragility in Si-PS without a host matrix, comparisons may be made with reports on polymer-grafted nanoparticles within a host matrix. Oh and Green49 used DSC to measure fragility of PS nanocomposites containing Au-PS nanoparticles. They investigated two Au-PS samples with graft MWs of 1 and 48 kg/mol. In nanocomposites using Au-PS with 1 kg/mol grafts, fragility decreased from 106 in neat PS to ∼82 at 0.5 wt % AuPS in PS. In nanocomposites using Au-PS with 48 kg/mol grafts, fragility decreased to ∼99 at 1.5 wt % Au-PS in PS.49 It is important to note that in their study the matrix PS had a MW of 5 kg/mol, so the reported fragility of the neat PS is 106. Although the fragility of the nanocomposites exhibited small reductions, their data may suggest that Au-PS nanoparticles themselves exhibited reduced fragility relative to PS free chains and also that fragility in PS-grafted nanoparticles decreased with decreasing MW. The interpretation agrees qualitatively with results in Figure 5B. The results of this study may be compared with simulations of nanocomposites. Betancourt et al.65 used molecular dynamics simulations to investigate the impact of attractive and nonattractive interactions on Tg and fragility in nanocomposites containing bare nanoparticles. They reported enhancements in Tg and fragility for particle/matrix pairs with attractive interactions and reductions in Tg and fragility for particle/matrix pairs with nonattractive interactions. Based on their predictions, the Si-PS samples (without a matrix) exhibit Tg and fragility behavior that is consistent with nonattractive particle/matrix pairs. This result suggests that covalent attachment of chain ends to nanoparticles is not analogous to particle/matrix pairs that exhibit attractive interactions. This is in agreement with results of Akcora et al.,101,102 who have indicated that the “dislike” between PS grafts and the nanoparticle cores is retained despite covalent attachment. A comparison of the fragility results from Si-PS may be made to those from brushes on flat silica substrates. Using

4. CONCLUSIONS Glass transition behavior of PS-grafted silica nanoparticles without a host polymer matrix is investigated by DSC. Tg values (both Tg,onset and Tf) decrease as a function of decreasing graft MW, in agreement with reports in the literature.39−41 Reductions in Tg are attributed to the impact of free chain ends in enhancing conformational mobility of polymer chains. At the same MW, Si-PS exhibited greater Tg relative to PS free chains due to chain tethering. DSC is also used to determine that Tg breadth is invariant within error with decreasing graft MW down to 36 kg/mol and increases for graft MWs of 12 and 13 kg/mol. The enhanced Tg breadth of low-MW Si-PS can be understood to arise from greater reduction in local Tg associated with the free chain ends relative to the local Tg associated with the grafted ends. Using fluorescence spectroscopy, we find that Tg is ∼116 °C within 8 kg/mol of the graft interface (total brush Mn = 54 kg/mol) and is ∼102 °C within 14 kg/mol of the free chain ends (total brush Mn = 93 kg/mol). The MW dependence of fragility in Si-PS without a host matrix is investigated for the first time using DSC. With reductions in graft MW, fragility of Si-PS decreases to a greater extent than in unattached PS. This result is attributed to the enhanced ability of free chain ends to impact chain packing in Si-PS relative to unattached PS and is in contrast to results on densely grafted PS brushes on flat silica substrates, which show no MW dependence of brush fragility for the brush MWs under investigation.103

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AUTHOR INFORMATION

Corresponding Author

*(J.M.T.) E-mail: [email protected]. ORCID

John M. Torkelson: 0000-0002-2273-5396 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We acknowledge the support of the National Science Foundation (Award No. 1235355) and a 3M Fellowship (to S.A.). This study made use of Central Facilities supported the NSF-MRSEC program (Grant DMR-1121262) at Northwestern University.

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DOI: 10.1021/acs.macromol.7b00079 Macromolecules XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.macromol.7b00079 Macromolecules XXXX, XXX, XXX−XXX